One-step production of 1,3-propanediol from ethylene oxide and syngas with a catalyst with a N-heterocyclic ligand

ABSTRACT

Disclosed is a new catalyst composition comprising a bimetallic Co-Ru catalyst complexed with a N-heterocylcic ligand that is effective, economical, and provides improvements in oxidative stability in the one step synthesis of 1,3-propanediol (1,3-PDO) from ethylene oxide and synthesis gas. For example, cobalt-ruthenium-2,2&#39;-bipyrimidine, 2,2&#39;-dipyridyl, or 2,4,6-tripridyl-s-triazine catalyst precursors in cyclic ether solvents, such as 1,3-dioxolane, 1,4-dioxolane, 1,4-dioxane, and 2-ethyl-2-methyl-1,3-dioxolane, provide good yields of 1,3-PDO in a one step synthesis.

This application claims the benefit of U.S. Provisional Application No.60/291,826 filed May 18, 2001, the entire disclosure of which is herebyincorporated by reference.

FIELD OF INVENTION

This invention relates to the synthesis of an aliphatic 1,3-diol,particularly 1,3-propanediol, from ethylene oxide and syngas in onestep. More particularly this invention relates to a catalyst thatprovides good yields under mild conditions in the one-step synthesis of1,3-propanediol and demonstrates advantages with respect to cost andoxidative stability. The catalyst of the invention comprises ahomogeneous bimetallic cobalt-ruthenium catalyst, plus a N-heterocyclicligand, or multidentate N-heterocyclic ligand.

BACKGROUND OF THE INVENTION

Aliphatic 1,3-diols, particularly 1,3-propanediol, have manyapplications as monomer units for polyester and polyurethane, and asstarting materials for the synthesis of cyclic compounds. For example,CORTERRA® polymer is a polyester characterized by outstanding propertiesthat is made of 1,3-propanediol (hereafter 1,3-PDO) and terephthalicacid. There is much interest in the art in finding new routes forsynthesizing 1,3-PDO that are efficient, economical, and demonstrateprocess advantages.

U.S. Pat. Nos. 3,463,819 and 3,456,017 teach the hydroformylation ofethylene oxide to produce 1,3-propanediol and 3-hydroxypropanal(hereafter 3-HPA) using a tertiary phosphine-modified cobalt carbonylcatalyst.

U.S. Pat. No. 5,304,691, assigned to Shell, discloses a method ofhydroformylating ethylene oxide to 3-hydroxypropanal and 1,3-propanediolin a single step using an improved catalyst system comprising acobalt-tertiary phosphine ligand in combination with a rutheniumcatalyst. In '691 1,3-PDO and 3-HPA are produced by intimatelycontacting an oxirane, particularly ethylene oxide (hereafter EO), aditertiary phosphine-modified cobalt carbonyl catalyst, a rutheniumcatalyst promoter, and syngas (carbon monoxide and hydrogen) in an inertreaction solvent at hydroformylation reaction conditions. A PDO yield ofup to 86-87 mole % is reported, using a catalyst comprising cobaltligated with 1,2-bis (9-phosphabicyclononyl) ethane as bidentate ligand,and either triruthenium(0) dodecacarbonyl or bis[ruthenium tricarbonyldichloride] as cocatalyst.

The production of 1,3-PDO in one step with minimal impurities andbyproducts involves recycle and requires a catalyst system with goodstability both during 1,3-PDO synthesis and during product recovery andrecycle. It would be very desirable if a catalyst system were availablethat produced 1,3-PDO in one step, in good yields, and was characterizedby greater oxidative stability during 1,3-PDO synthesis and recycle. Inaddition, phosphine ligands are relatively expensive and it would bedesirable to have the option of a ligand system that provided theaforementioned advantages, but was less expensive.

SUMMARY

In accordance with the foregoing, the present invention provides analternative to the use of phosphine ligands in a hydroformylationcatalyst composition. The ligands of the present invention provide aless expensive alternative, have the ability to form stable complexeswith Group VIII transition metals, and provide good oxidative stability.The invention is a catalyst composition comprising:

a) A cobalt component comprising of one or more non-ligated cobaltcarbonyl compounds; and

b) A ruthenium component comprising a ligated ruthenium carbonylcompound wherein said ligand is selected from a N-heterocyclic ormultidentate N-heterocyclic moiety.

Bidentate and multidentate N-heterocyclics offer the potentialadvantages of greater oxidative stability, commercial availability (atleast in certain cases), potentially lower cost, and the ability to formstable complexes with Group VIII transition metals. For example,2,2′-dipyridyl-ruthenium complexes, among others, have been demonstratedto exhibit long-term stability under hydroformylation (synthesis gaspressure conditions).

The novel oxirane hydroformylation catalyst of the present inventioninvolves a complex which is postulated to be a ruthenium-N-heterocylicligand: cobalt complex. The characterizing feature of the new catalystis the use of a bidentate or multidentate N-heterocyclic ligand ligatedto ruthenium rather than cobalt, as is the case in U.S. Pat. No.5,304,691.

The invention also provides a one step process for preparing a 1,3-diol,comprising the reaction of an oxirane with syngas at hydroformylationconditions in an inert solvent in the presence of the catalyst complexof this invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an IR spectrum of thecobalt-ruthenium-2,4,6-tripyridyl-s-triazine (TPTZ) catalyst afterpreforming in 1,3-dioxolane.

FIG. 2 is an IR cascade plot showing the formation of the Co—Ru-TPTZcatalyst as a function of time.

FIG. 3 shows the IR spectrum of the Co—Ru-TPTZ catalyst during theone-step conversion of ethylene oxide and synthesis gas to1,3-propanediol.

FIG. 4 is an IR cascade plot showing the Co—Ru-TPTZ catalyst during theone-step 1,3-PDO synthesis.

FIG. 5 is a bar graph showing EO uptake times for thecobalt-ruthenium-2,2′-dipyridyl catalyst, solubilized in 1,3-dioxolane,when used for 1,3-propanediol one-step syntheses.

DETAILED DESCRIPTION OF THE INVENTION

The selective hydroformylation/hydrogenation of ethylene oxide to1,3-PDO in one step, represented by:

 

has been demonstrated using a cobalt-ruthenium homogeneous catalystsystem in conjunction with soluble bidentate or multidentateN-heterocyclic ligands. N-heterocyclic ligands that provide goodresults, include, for example, the commercially available2,2′-dipyridyl, 2,2′-bipyrimidine, and 2,4,6-tripyridyl-s-triazine.

The one-step process for synthesizing 1,3-PDO generally comprisesintimately contacting ethylene oxide, carbon monoxide and hydrogen(syngas), and a bimetallic catalyst in a liquid-phase solution in aninert reaction solvent at a temperature of from about 30 to 150° C., andan elevated pressure.

The use of the new Co—Ru—N-heterocyclic system requires certainsynthesis changes in comparison with work where a phosphine ligand isligated to a Co compound, such as U.S. Pat. No. 5,304,691. Importantaspects of the one-step process of the present invention include theneed for particular solvents, the use of hydrogen-rich synthesis gas,and operation at a somewhat higher pressure. Preferred solvents includecyclic aliphatic ethers. Preferred operating pressure is closer to 2000psi (13,790 kPa), whereas in the case of the phosphine ligated Co thepreferred pressure is closer to 1500 psi (10,340 kPa).

Other important factors in the development of this chemistry includeefficient PDO recovery from the crude oxonated product solutions, andrecycle of the active Co—Ru—N-heterocyclic catalyst.

The 1,3-diols are made by charging an oxirane, catalyst, optionalcocatalyst and/or catalyst promoter, and reaction solvent to a pressurereactor with the introduction of syngas (a mixture of hydrogen andcarbon monoxide, suitably in a molar ratio of 1:1 to 8:1, preferably 2:1to 6:1) under hydroformylation conditions.

The process of the present invention may be carried out as a batch-typeprocess, continuous process, or a combination thereof.

In the preferred embodiment of the present invention separate, combined,or staged streams of EO, syngas, and catalyst are charged to a reactionvessel, which can be a pressure reaction vessel such as a bubble columnor a stirred autoclave, operated batch-wise or in a continuous manner.

Oxiranes of up to 10 carbon atoms, preferably up to 6 carbon atoms, andethylene oxide in particular may be converted into their corresponding1,3-diols by the hydroformylation reaction with syngas in the presenceof the catalyst complex of the present invention.

An essential part of the present invention is the use of theCo—Ru-bidentate or multidentate N-heterocyclic complex. The complex ofthe present invention is believed to comprise a novel class ofruthenium-modified catalysts. The characterizing feature of this novelclass involves an oxidized ruthenium metal that is ligated to abidentate or multidentate N-heterocyclic ligand, with a cobalt compoundas the counter ion.

The oxidation state of the ruthenium atom is not entirely certain (intheory, ruthenium may have a valence of 0 to 8), which may even changeduring the course of the hydroformylation reaction. Accordingly, themolar ratio of ruthenium to cobalt may vary within relatively broadranges. Sufficient cobalt(0) should be added to completely oxidize allof the complexed ruthenium employed. An excess of cobalt can be added,but is not of particular value. Suitably, the molar ratio varies from4:1 to 1:4, preferably from 2:1 to 1:3, more preferably from 1:1 to 1:2.

A large number of N-heterocyclic compounds have been identified assuitable ligands for the one step PDO synthesis using thecobalt-ruthenium catalyst couple. Suitable types of bidentate andmultidentate N-heterocyclic ligands include, but are not limited to:

Diazines such as pyrimidine, pyrazine, pyridazine, as well asbenzodiazines such as quinazoline and quinoxaline; bispyridines such as2,2′-dipyridyl (DIPY), 2,2′-bipyrimidine (BPYM), 1,10-phenanthroline(PHEN), di-2-pyridyl ketone, 4,4′-dimethyl-2,2′-dipyridyl,5,6-dimethylphenanthroline, 4,7-dimethylphenanthroline,2,2′-biquinoline, neocuproine, and 2,2′-dipyridylamine; multipyridinessuch as 2,4,6-tripyridyl-s-triazine (TPTZ),3,6-di-2-pyridyl-1,2,4,5-tetrazine, 2,2′:6′,2″-terpyridine,2,3-bis(pyridyl)pyrazine, and 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine;pyridine, 3-hydroxypyridine, and quinoline, particularly the lower costhomologues derived from coal-tar extracts; and certain2,6-pyridyl-diimines such as 2,6-bis(N-phenyl, methylimino)pyridine and2,6-bis [N-(2,6-diisopropylphenyl )methylimino]pyridine.

Good results were demonstrated in the examples herein using2,2′-dipyridyl (DIPY), 2,2′-bipyrimidine (BPYM), and2,4,6-tripyridyl-s-triazine (TPTZ). The structures of these threeN-heterocyclics are as follows:

 

Suitable cobalt sources also include salts that are reduced to the zerovalence state by heat-treatment in an atmosphere of hydrogen and carbonmonoxide. Examples of such salts comprise, for instance, cobaltcarboxylates such as acetates, octanoates, etc., which are preferred, aswell as cobalt salts of mineral acids such as chlorides, fluorides,sulfates, sulfonates, etc. Operable also are mixtures of these cobaltsalts. It is preferred, however, that when mixtures are used, at leastone component of the mixture be a cobalt alkanoate of 6 to 12 carbonatoms. The reduction may be performed prior to the use of the catalysts,or it may be accomplished simultaneously with the hydroformylationprocess in the hydroformylation zone.

The counter ion, for best results, is believed to be the cobalttetracarbonyl anion, ([Co(CO)₄]⁻), having a characteristic cobaltcarbonyl IR band in the region 1875 to 1900 cm⁻¹, particularly in theregion 1888 cm⁻¹. However, this ion in the active catalyst can be amodification thereof. Part of the cobalt compound may be modified withN-heterocyclic ligand, e.g., up to 75 mole % excess, say up to 50 mole %or less. However, the counter ion is preferably the non-ligated cobalttetracarbonyl anion mentioned before. Cobalt carbonyls can be generatedby reaction of a starting cobalt source such as cobalt hydroxide withsyngas, as described in J. Falbe, “Carbon Monoxide in OrganicSynthesis”, Springer-Verlag, NY (1970), which is herein incorporated byreference or otherwise.

The molar stoichiometry ratio of cobalt:ruthenium:N-ligand is suitablyin the range of 0.5 to 4 moles cobalt: 0.3 to 2 moles ruthenium: 0.1 to2 moles N-ligand. A preferred range would be about 1 to 3 moles cobaltto 0.5 to 1.5 moles ruthenium to 0.5 to 1 moles N-ligand. A formulationthat worked well, for example, was cobalt: ruthenium:2,4,6-tripyridyl-s-triazine in molar stoichiometry of 2: 1: 0.7,respectively. A preferred formulation is cobalt: ruthenium:2,2′-bipyrimidine or 2,2′-dipyridyl in a molar stoichiometry of 2:1:1 to1:1:1. Unligated ruthenium carbonyl is believed to be a far less activespecies, and the catalyst preparation therefore seeks to ligate eachruthenium atom.

The catalyst complex, can be made as follows: The first step in thecatalyst preparation is synthesis of the Ru—N-ligand complex. This maybe done by bringing a suitable Ru(0) source, e.g., trirutheniumdodecacarbonyl, in contact with the N-heterocyclic ligand.Alternatively, the triruthenium dodecacarbonyl may be replaced withother readily available ruthenium carbonyl derivatives, such asruthenium dicarbonyl acetate polymer and ruthenium(II) tricarbonyldichloride, dimer. Further alternatives include the use of lessexpensive ruthenium sources that, under a syngas atmosphere, willin-situ form ruthenium carbonyl species. These less expensive rutheniumsources may include ruthenium(IV) oxide, hydrate, ruthenium(III)chloride, and ruthenium-on-carbon.

The conditions at which these compounds are allowed to form a complexare not critical. Temperature and pressure may vary within the rangesgiven below with respect to the hydroformylation reaction, for example25 to 150° C. Syngas may be used as gas cap during the complexformation. It is preferable to use a solvent, preferably the solventused in the hydroformylation reaction. Obviously, this solvent should becapable of dissolving the active catalyst, without affecting itsproperties. Suitable solvents include the ethers described below for usein the hydroformylation process, in particular cyclic aliphatic ethers.

The ruthenium-N-heterocyclic ligand may for instance be made by reactingtriruthenium dodecacarbonyl with a stoichiometric amount of a selectedN-heterocyclic ligand in a solvent at a temperature within the range of25 to 150° C., suitably 100 to 110° C. under a carbon monoxide orsynthesis gas atmosphere, for 1 to 24 hours (i.e. until completion). Atthis point, optionally, said ruthenium-N-heterocyclic complex may beisolated as a discrete material.

Next, the Ru—N-heterocyclic ligand complex is brought into contact witha suitable cobalt carbonyl compound by means of a redox reaction to formthe Ru—Co—N-ligand complex, again at the aforementioned (noncritical)conditions. A suitable cobalt source is dicobalt. octacarbonyl, butother cobalt complexes and salts may be used as well. For instance, theselected cobalt carbonyl, and optional promoters, if any, are added tothe solution which is then maintained at the elevated temperature (from25 to 150° C.) for a time of about 15 minutes to 24 hours. This processis referred to as a step-wise preparation method. Again, optionally, thenew cobalt-ruthenium-N-heterocyclic complex may be isolated andcharacterized.

It is also within the scope of the present invention to prepare thecobalt-ruthenium-N-heterocyclic complex by a self-assembly method,wherein all catalyst components are brought together at the same time.The cobalt-ruthenium-N-heterocyclic complexes may be generated byself-assembly, in one step, when solubilized in a suitable ether solventunder synthesis gas conditions, but the conditions and, in particular,the solvent, are selected such as to favor the formation of a ligatedruthenium species, rather than a ligated cobalt species. The presence ofthe Ru-ligated species rather than the Co-ligand species may beconfirmed by e.g. IR analysis. Typically, whether said activeCo—Ru—N-heterocyclic catalyst is generated step-wise, or by selfassembly, it exhibits characteristic IR bands in the metal-carbonylregion, particularly a strong cobalt carbonyl band in the region 1875 to1900 cm⁻¹ due to the [Co(CO)₄]⁻ anion, plus a series of three or fourruthenium-carbonyl bands in the 1900 to 2100 cm⁻¹ region that arepostulated to be due to cationic ruthenium carbonyl species. Typicalspectra for the Co—Ru-TPTZ catalyst system in 1,3-dioxolane, both duringthe preparation of said catalyst, and during the EO/syngas reaction togive 1,3-PDO, are illustrated in the accompanying FIGS. 1-4.

The optimum ratio of oxirane in the feed to Ru—Co—N-ligand complex willin part depend upon the particular complex employed. However, molarratios of oxirane to the cobalt within the Ru—Co—N-ligand complex from2:1 to 10,000:1 are generally satisfactory, with molar ratios of from50:1 to 500:1 being preferred.

The reaction solvent should be inert, meaning that it is not consumedduring the course of the reaction. Ideal solvents for the inventionprocess will solubilize the feed and products during the course of thereaction, but allow phase separation at reduced temperatures. Suitablesolvents are described in U.S. Pat. No. 5,304,691 incorporated herein byreference in the entirety. Good results may be achieved with ethers,particularly cyclic, aliphatic ethers, optionally in combination with analcohol, such as ethanol or tert-butanol, and/or an aromatichydrocarbon, such as toluene and the chlorobenzenes.

The summary data in Tables 1 and 2 illustrate the important yield andselectivity advantages of using certain cyclic ether solvents such as,for example, but not limited to, the five-membered ring, 1,3-dioxolane,the six-membered ring, 1,3-dioxane, and 1,4-dioxane (see examples 1 to16), versus a non-cyclic ether such as methyl tert-butyl ether (MTBE,see example 17). 1,3-Dioxane is of particular interest since it can bereadily generated through condensation of 1,3-PDO with formaldehyde.2-Ethyl-2-methyl-1,3-dioxolane proved to be a particularly interestingsolvent choice since it allows PDO product phase separation under normaloperating conditions (see example 16). Here the PDO is concentrated in aPDO-rich phase in ca. 36% concentration. The estimated 1,3-PDO yield is58 mole % and the PDO selectivity 54-73%.

Promoters may be employed. Suitable promoters are described in U.S. Pat.No. 5,304, 691, previously cited. Examples of promoters that work well,are readily available, and have demonstrated the promotion of EOconversion are tertiary amines such as N,N-dimethyldodecylamine andtriethylamine, as well as alkali salts such as sodium acetate.

For best results, the one step hydroformylation/hydrogenation isconducted under conditions of elevated temperature and pressure.Reaction temperatures range from 30 to 150° C., preferably from 50 to125° C., and most preferably from 60 to 110° C.

The reaction pressure (total pressure, or partial pressure if inertgaseous diluents are used) should be at least 100 psi (690 kPa). Asuitable operating pressure is in the range of 100 psi (690 kPa) to 4000psi (27,580 kPa), preferably from 1500 psi (10,340 kPa) to 2500 psi(17,240 kPa), and most preferably about 2000 (13,790 KpA) psi ±250 psi(1725 kPa). In a batch process, the reaction will generally be completewithin 1.5 to 5 hours.

The components of the feed streams are contacted in a suitable reactionsolvent in the presence of the catalyst complex of the presentinvention. The EO will preferably be maintained throughout the reactionin a concentration not less than about 0.2% by weight, generally withinthe range of 0.2 to 20% by weight, preferably 1 to 10% by weight, basedon the total weight of the reaction mixture. The process of theinvention can be carried out in a continuous mode, while maintainingsaid EO concentration, by for instance, staged EO addition.

At the conclusion of the hydroformylation reaction, the product mixtureis recovered by conventional methods such as selective extraction,fractional distillation, phase separation, selective crystallization,and the like. The unreacted starting materials as well as the catalystand reaction solvent may, and preferably are, recycled for further use.

Partitioning of the reaction mixture can be promoted by the addition ofa phase-split inducing agent. Suitable agents include glycols such asethylene glycol and linear alkanes such as dodecane. Such an agent willbe added to the reaction mixture in an amount within the range of about2 to 10% by weight, preferably 4 to 8% by weight, based on the totalreaction mixture. Alternate methods include addition of 1,3-propanediolinto the reaction mixture to bring product concentration up to thetarget proportion. Also, miscibilizing alcohols and agents with similarpolarity such as ethanol, propanol and isopropanol can be addedinitially, and then removed prior to the subsequent inducing of thephase separation.

Commercial operation will require efficient catalyst recovery withmultiple cycles of essentially complete recycle of catalyst to thereaction. The preferred catalyst recovery process involves separation ofthe two liquid phase mixture noted previously and recycle of the bulksolvent phase to the reactor and return therewith of at least 60 to 90%by weight of the starting catalyst.

In a preferred manner of running the process, reaction conditions suchas oxirane concentration, catalyst concentration, solvent, productconcentration, reaction temperature and the like are selected so as toachieve a homogeneous reaction mixture at elevated temperatures andcause a partitioning of the reaction mixture into an upper solvent phasecontaining much of the catalyst and a lower phase containing most of the1,3-propanediol upon cooling the mixture. Such a partitioningfacilitates isolation and recovery of product, recycle of catalyst andremoval of heavy ends from the solvent system. This process is referredto as a phase separation catalyst recycle/product recovery method.

In this process, the reactor contents are allowed to settle or aretransferred to a suitable vessel at pressures ranging from atmosphericto near reaction pressure where, upon slight or considerable cooling,distinct phases may form that are substantially different, beingconsiderably rich in product, or in catalyst and solvent. The phase richin catalyst and solvent is directly recycled for further reaction withfeed materials. Product is recovered from the product rich phase byconventional methods.

It is preferable that the reaction is run such that product diolmaintains concentration levels in the reaction mix suitable for phaseseparation. For example, concentration of 1,3-propanediol can be betweenless than 1 and greater than 50% by weight, generally between 8 and 32%by weight, and preferably between 16 and 20% by weight. Temperatureduring quiescent settling of phases can be between just above thefreezing point of the reaction mixture up to at least 150° C., and maybehigher, generally between 27 and 97° C., and preferably between 37 and47° C. The EO concentration is maintained to avoid the formation oflight alcohols and aldehydes that are miscibilizing agents. Oxiraneswill preferably be maintained throughout the reaction in a concentrationnot less than about 0.2% by weight, generally within the range of 0.2 to20% by weight, preferably 1 to 10% by weight, based on the total weightof the reaction. The reaction can be run with a two-phase system.However, yields and selectivities are maximized when high concentrationsof product are present in a single phase reaction and subsequent phaseseparation occurs upon cooling.

Formulations containing both bidentate and multidentate ligandsperformed well. Good results have been demonstrated with bimetalliccobalt-ruthenium catalysts in combination with a variety of bidentateN-heterocyclic ligands when solubilized in suitable ether solvents. Thecobalt-ruthenium-2,2′-bipyrimidine and 2,2′-dipyridyl catalystprecursors are particularly effective (see, for example, the data inTables 1 and 2).

Good results have also been realized with multidentate N-heterocyclicligands, for example, using thecobalt-ruthenium-2,4,6-tripyridyl-s-triazine (TPTZ) catalyst precursor,in cyclic ether solvents such as 1,3-dioxolane, 1,3-dioxane,1,4-dioxane, and 2-ethyl-2-methyl-1,3-dioxolane (again see data in Table1).

An in situ infra-red study of thecobalt-ruthenium-2,4,6-tripyridyl-s-triazine catalyst in 1,3-dioxolane(example 58, Table 10), shows the formation of four characteristic bandsin the metal-carbonyl region at 1888, 1950, 1986, and 2015 cm⁻¹ duringpreforming of the active species at 90° C. under synthesis gas (CO/H₂,1:4). After addition of ethylene oxide, the reaction mixture at 90° C.,again under synthesis gas pressure, continues to exhibit a strong bandat 1888 cm⁻¹, plus additional bands at 1950, 1984, 2015, and 2048 cm⁻¹.This band pattern remains during 1,3-propanediol formation. Typical IRspectra, plus cascade plots, are shown in FIGS. 1-4.

The following examples will serve to illustrate the invention disclosedherein. The examples are intended only as a means of illustration andshould not be construed as limiting the scope of the invention in anyway. Those skilled in the art will recognize many variations that may bemade without departing from the spirit of the disclosed invention.

EXAMPLES 1-20

Examples 1-20 were conducted in a 300 cc capacity Parr reactor system,integrated into a syngas manifold. In examples 1-12 the N-heterocyclicligand is varied, but only two cyclic ether solvents are employed. Inexamples 13-20 the solvent is varied. Variations in other components andconditions are noted. Data are given in Tables 1 and 2.

As previously mentioned, particularly good results were demonstratedusing 2,2′-dipyridyl (DIPY), 2,2′-bipyrimidine (BPYM), and2,4,6-tripyridyl-s-triazine (TPTZ). Summary data for the use of thesethree N-heterocyclics, plus 1,10-phenanthroline (PHEN), in the one-stepPDO synthesis are provided in Table 1. Here PDO yields are calculated ona molar basis, based upon the quantity of ethylene oxide charged, whilePDO selectivities are estimated by gas chromatograph (GC) analysis ofthe crude product fractions. The primary co-products include ethanol(the major co-product fraction), HPA intermediate, acetaldehyde, and asmall quantity of heavies that include 3-hydroxypropyl-2-hydroxyethylether, 3-hydroxypropyl 3-hydroxypropionate, and a PDO/EG ester of3-hydroxypropionate (all confirmed by GC-ms/IR). The promoter wasN,N-dimethyldodecylamine (Me₂C₁₂N). In Table 1, example 1, conducted at90° C. with 1800 psi (12,410 kPa) of ½ (CO/H₂) syngas, the 1,3-PDO yieldis 49 mole %, basis EO charged, the PDO/HPA product ratio is 26, and the1,3-PDO/EtOH ratio is 9. Acetaldehyde concentration in the crude productliquid is only 0.3%. In the first Co—Ru-DIPY example (see example 2,Table 1), conducted at 90° C., with 2000 psi (13,790 kPa) of ¼ (CO/H₂)syngas, the 1,3-PDO molar yield is 54%, the estimated PDO/ethanol wtratio is 13, the PDO/HPA ratio is ca. 2.8, and the acetaldehydeconcentration in the crude product liquid is 0.8%. Total PDO plus HPAmolar yield is ca. 74%, while the dark purple product solution shows nosigns of precipitates and the reactor is clean. Multiple ethylene oxideadditions, (as in example 5), raise the PDO yield to 66 mole %, and herethe PDO/HPA ratio in the final product is >100.

With TPTZ as the added N-heterocycle, hydrogenation of the intermediateHPA is near quantitative and in both examples 7 and 8 the PDO/HPA ratiois >100. 1,3-PDO yields are typically 57-59 mole %. Using 1,4-dioxane asthe solvent, as in example 8, the 1,3-PDO/EtOH ratio is 7 and theacetaldehyde make is also below 0.1%. Basis in situ IR studies, we seeno evidence for precipitates with this N-heterocycle, either during theCo—Ru-TPTZ catalyst preparation stage, or during the PDO generationphase. Product distributions were again confirmed by GC-ms/IR.

A particular advantage in the use of 2,2′-dipyridyl is that it iscommercially available from, for example, Zeneca Corporation orSigma-Aldrich. A sample of DIPY (97% purity) from Zeneca Corporation(see example 9, Table 1, PDO/HPA ratio 6.6, PDO/EtOH ratio 14) performedsimilarly to our original samples from Aldrich. Further purification ofthe Zeneca material through hexane recrystallization (m.p. 69-71° C.)had only a marginal effect upon its performance in PDO service (seeexample 10, PDO/HPA ratio again 6.6). A second improvement in costs maybe realized by using ruthenium dioxide, hydrate as the ruthenium sourceand generating the ruthenium carbonyl precursors in situ (example 11) bypretreatment at 160° C. with CO-rich gas, PDO+HPA molar yields arethen >65%, PDO/EtOH ratio is 15, and acetaldehyde concentration 0.5%.Another alternative is to use ruthenium-on-carbon (example 12, fromAlfa), although here the supernatant liquid product typically shows ca.910 ppm ruthenium.

TABLE 1 CATALYST PDO YIELD EXP. COMPOSITION Co:Ru:N SOLVENT Me₂C₁₂NCONDITIONS PDO SEL. (%) (mole %) 1 Co₂(CO)₈— 2:1:2 1,3-dioxolane No a 6149 Ru₃(CO)₁₂— BPYM 2 Co₂(CO)₈— 1:1:2 ″ Yes b 61 54 Ru₃(CO)₁₂— DIPY 3Co₂(CO)₈— 1:1:2 ″ Yes, c b 56 51 Ru₃(CO)₁₂— DIPY 4 Co₂(CO)₈— 1:1:3 ″ Yesb 69 57 Ru₃(CO)₁₂— DIPY 5 Co₂(CO)₈— 1:1:2 ″ Yes, c b, d 74 66 Ru₃(CO)₁₂—DIPY 6 Co₂(CO)₈— ″ ″ Yes b 38 29 Ru₃(CO)₁₂— PHEN 7 Co₂(CO)₈— 1:1:e,f ″Yes, c b 71 57 Ru₃(CO)₁₂— TPTZ 8 Co₂(CO)₈— 1:1:e 1,4-dioxane Yes b 76 59Ru₃(CO)₁₂— TPTZ 9 Co₂(CO)₈— 1:1:2 1,3-dioxolane Yes, c b 70 53Ru₃(CO)₁₂— DIPY, g 10 Co₂(CO)₈— ″ ″ Yes, c b 69 56 Ru₃(CO)₁₂— DIPY, h 11Co₂(CO)₈— ″ ″ Yes, c b 70 55 RuO₂— DIPY 12 Co₂(CO)₈— ″ ″ Yes, c b 71 5510% Ru/C— DIPY a Run conditions: 90° C., 1800 psi (12,410 kpa), ½(CO/H₂₎ a Run conditions: 90° C., 2000 psi (13,790 kpa), ¼ (CO/H₂₎ cDouble promoter concentration d Scale-up run, made in 300 cc capacitybatch reactor, four ethylene oxide additions e Ratio is 1:1:1,Co:Ru:TPTZ f Double catalyst concentration g DIPY from Zeneca Corp. hDIPY from Zeneca, recrystallized from hexane

 

TABLE 2 CATALYST PDO SEL. PDO YIELD EXP. COMPOSITION Co:Ru:N SOLVENTMe₂C₁₂N CONDITIONS (%) (mole %) 5 Co₂(CO)₈— 1:1:2 1,3-dioxolane Yes a 7466 Ru₃(CO)₁₂— DIPY 13 Co₂(CO)₈— ″ 1,3-dioxane, c Yes a 67 54 Ru₃(CO)₁₂—DIPY, b 14 Co₂(CO)₈— ″ 1,3-dioxane, Yes a 72 63 Ru₃(CO)₁₂— c,d DIPY, b15 Co₂(CO)₈— ″ 1,4-dioxane Yes a 71 47 Ru₃(CO)₁₂— DIPY, b 16 Co₂(CO)₈— ″2-ethyl-2- Yes e 54-73, f 58 Ru₃(CO)₁₂— methyl-1,3- DIPY, b dioxolane 17Co₂(CO)₈— ″ MTBE Yes a 36 21 Ru₃(CO)₁₂— DIPY, b 18 Co₂(CO)₈— 2:1:2 THFYes g N.D. 4.5 Ru₃(CO)₁₂— DIPY, b 19 Co₂(CO)₈— 1:1:2 N—(Me₂—N-ethyl)-Yes a N.D. <1 Ru₃(CO)₁₂— morpholine DIPY, b 20 Co₂(CO)₈— ″ Sulfolane Yesa 37 14 Ru₃(CO)₁₂— DIPY, b a Run conditions: 90° C., 2000 psi (13,790kpa), ¼ (CO/H₂) b Catalyst concentration increased by 1.5 c 1,3-Dioxanefrom Ferro Corporation d Larger batch, 99.8% purity e Run conditions:100° C., 2000 psi (13,790 kpa), ¼ (CO/H₂) f Two-phase product liquid,PDO concentrated in the heavier phase g Run conditions: 90° C., 1500 psi(10,340 kpa), ½ (CO/H₂)

 

EXAMPLE 21

In Example 21 a typical life study of the catalyst complex wasconducted. Dicobalt octacarbonyl-trirutheniumdodecacarbonyl-2,2′-dipyridyl catalyst solubilized in 1,3-dioxolane wasused as the catalyst precursor for eighteen EO additions and four PDOdistillations. Here the initial Co—Ru-DIPY stoichiometry was 1:1:1 andeach EO hydroformylation was conducted at 90° C. under 2000 psi (13,790kPa) of ¼ (CO/H₂) syngas. The typical operating procedures are asfollows:

1. Four EO additions to the Co—Ru—N-heterocyclic catalyst solubilized ina cyclic ether solvent, with hydroformylation/hydrogenation of each EOaddition to PDO as detailed previously.

2. PDO recovery by vacuum distillation after solvent stripping.

3. Recycle of the bottoms Co—Ru—N-heterocyclic catalyst solution in PDO,with fresh ether solvent. Data are given in Table 3:

TABLE 3 # EO PDO Yield PDO Sel. Distilled PDO Additions (mole %) (%)PDO/EtOH (gm) 4 66 74 5.0 15 4 49 73 6.8 38 4 52 67 7.9 49 4 69 57 5.831 2 52 44 11.3  N.D.

 

Generally, we have found that as the number of cycles increases there isa slow build-up of organic heavies, particularly3-hydroxypropyl-2-hydroxyethyl ether, 3-hydroxypropyl3-hydroxypropionate, and the PDO/EG esters of 3-hydroxypropionate(identified by GC-ms/IR). With constant liquid sampling, we are alsodepleting the system of catalyst, so that the time to complete each EOuptake is stretched from 4 to 9 hours. All product solutions exhibitvery little residual HPA (<1%) and acetaldehyde exit concentrationsnever rise above 0.4%. After 18 EO additions the final product is aclear, deep red liquid, with no evidence of precipitates. Cobalt andruthenium recoveries are 68% and 64%, respectively, basis metalsanalyses (X-ray florescence). Likewise, inspecting the reactor after 5weeks of operation, it is clean, with no residual solid.

EXAMPLE 22

An experimental series very similar to that of Example 21 was alsoperformed where the intermediate solids formed during the multi-cyclingprocess were removed by filtration (prior to PDO distillation) and after18 EO additions a small quantity of make-up catalyst was added. Anadditional four EO additions were completed, making a grand total of 22.EO uptake times for this second catalyst life study are illustrated inFIG. 5.

EXAMPLES 23-98

A series of cobalt-ruthenium homogeneous catalysts in association with anumber of N-heterocyclic ligands were employed for one-step 1,3-PDOsynthesis, using different molar ratios of components of catalystcomplex, various solvents, and a range of reaction conditions. Theseruns were conducted in 100 cc capacity batch reactors, hooked to asynthesis gas manifold, and having the appropriate temperature/pressurereadouts and controls. These data illustrate the use of:

A series of N-heterocyclic ligands including 2,2′-bipyrimidine (BPYM),2,2′-dipyridyl (DIPY), 2,4,6-tripyridyl-s-triazine (TPTZ),1,10-phenanthroline, 2,2′-biquinoline, 2,2′-dipyridylamine, di-2-pyridylketone, 4,7-dimethylphenanthroline, 5,6-dimethylphenanthroline,pyrimidine, pyridazine, quinazoline, neocuproine,3,6-di-2-pyridyl-1,2,4,5-tetrazine, 2,2′:6′,2″-terpyridine, and3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine.

A series of ruthenium precursors including triruthenium dodecacarbonyl,ruthenium(IV) oxide, and 10% ruthenium-on-carbon.

A range of ether solvents including MTBE, tetrahydrofuran (THF),1,3-dioxolane, 1,4-dioxolane, dimethyl-1,3-dioxolane,4-methyl-1,3-dioxolane, 2-ethyl-2-methyl-dioxolane, and 1,4-dioxane.

Promoters including triethylamine and N,N-dimethyldodecylamine, as wellas sodium acetate.

Experimental data are summarized in the following Tables 4-19 for thisdirect, one-step, conversion of ethylene oxide plus synthesis gas to1,3-propanediol. In the Product Phases column, T is the top phase, B isthe bottom phase, and P is the total product when only one phase ispresent.

TABLE 4 Time PDO PDO PDO EO Uptake Product Conc. (%) Production Sel.Yield EXP. Catalyst Solvent Temp ° C. (hrs) Phases wt (g) PDO HPA(mmole) (%) (mole %) 23 Co₂(CO)₈— MTBE 90 3 T 18.3 1.4^(d,e) 0.1^(e) 4.626 13 Ru(CO)₁₂ B 1.2 32.2^(e) 0.7^(e) 2.7 48 BPYM W/W 4.5 0.2 3.0 10.324 Co₂(CO)₈— MTBE 80 3.5^(a) P^(c) 19.0 1.0 0.4 4.0 N.D. 6.4 Ru(CO)₁₂W/W 2.3 1.0 1.5 BPYM 5.5 25 Co₂(CO)₈— MTBE 90 2.5 P 18.9 1.1 1.0 4.4N.D. 8.3 Ru(CO)₁₂ W/W 3.7 2.0 2.6 BPYM^(b) 7.0 26 [Ru₂(CO)₄ MTBE 804^(a) P^(g) 18.7 0.3 0.1 0.9 N.D. 1.1 (MeCOO) W/W N.D. N.D. N.D.(PBYM)₂]^(+f) 0.9 27 Ru₃(CO)₁₂- Tol/ 90 1.75^(a) P 23.2 0.2 N.D. 0 N.D.4.8 BPYM ClC₆H₅ W/W^(j) 5.1^(d) N.D. 3.9 3.9 28 [Ru₂(CO)₄ MTBE 90 2^(a)P 18.5 1.2 0.1 4.3 N.D. 5.4 (MeCOO) W/W N.D. N.D. N.D. (BPYM)₂]^(+b,h)4.3 ^(a)Run with ½ (CO/H2) gas ^(b)Run with no NaOAc promoter ^(c)Someheavy catalyst residue in bottom of reactor ^(d)Checked by PDO spiking^(e)Confirmed by GC-ms/IR ^(f)Product 24090-119 ^(g)Large quantity ofcatalyst residue ^(h)Product 24090-135 ^(i)Lot of solids in water wash

 

TABLE 5 Time PDO PDO PDO EO Uptake Product Conc. (%) Production Sel.Yield EXP. Catalyst Solvent Temp ° C. (hrs) Phases wt (g) PDO HPA(mmole) (%) (mole %) 29 Co₂(CO)₈— THF 90 4^(a) P 23.2 2.8 0.1 12.5 45 15Ru₃(CO)₁₂ W/W N.D. N.D. N.D. BPYM 12.5 30 Co₂(CO)₈— 1,3- 90 3^(a) P 27.15.8 0.3 21.7 51 29 Ru₃(CO)₁₂ dioxolane W/W^(c) N.D. N.D. N.D. BPYM^(d)21.7 31 Co₂(CO)₈— THF 90 1.5^(a,b) P 22.3 N.D. 1.0 N.D. N.D. <0.1Ru₃(CO)₁₂ W/W N.D. N.D. N.D. BPYM N.D. 32 2[Co₂(CO)₈— 1,3- 90 2.5^(a) P29.1 N.D.^(f) 1.2 N.D. N.D. <0.1^(f) Ru₃(CO)₁₂ dioxolane W/W N.D. N.D.N.D. BPYM] N.D. 33 Co₂(CO)₈— 1,4- 90 1.75^(d) P 26.7 0.2 ^(e) 1.1 N.D.1.3 Ru₃(CO)₁₂ dioxolane W/W N.D. ^(e) N.D. BPYM 1.1 34 Co₂(CO)₈— 1,3- 903.25^(a) P 27.5 5.6 1.0 23.0 51 29 Ru₃(CO)₁₂ dioxolane W/W N.D. N.D.N.D. BPYM 23.0 Me₂C₁₂H₂₅N ^(a)Run with ½ (CO/H2) gas ^(b)Half the usualEO charge ^(c)Small quantity of supension in water wash ^(d)New batch of2,2-bipyrimidine ^(e)Could not be determined, HPA and 1,4-dioxane havethe same glc retention time ^(f)Repeat run -185R gave very similar data

 

TABLE 6 Time PDO PDO PDO EO Uptake Product Conc. (%) Production Sel.Yield EXP. Catalyst Solvent Temp ° C. (hrs) Phases wt (g) PDO HPA(mmole) (%) (mole %) 35 Co₂(CO)₈— THF 90 3^(b) P 23.5 2.4 1.1^(e) 9.9 30 12^(e) Ru₃(CO)₁₂ W/W N.D. N.D. N.D. BPYM^(a) 9.9 36 Co₂(CO)₈— 1,3- 902.5^(b) P 28.0 2.1 3.7 8.5 22 11 2[Ru₃(CO)₁₂ dioxolane W/W N.D. N.D.N.D. BPYM] 8.5 37 2[Co₂(CO)₈— 1,3- 90 2.5^(b) P 52.2 N.D. 1.3 N.D. N.D.<0.1 Ru₃(CO)₁₂ dioxolane W/W N.D. N.D. N.D. BPYM]^(c) N.D. 38 Co₂(CO)₈—1,3- 90 3^(b) P 28.0 6.9 0.4 26.7 57 36 Ru₃(CO)₁₂ dioxolane W/W N.D.N.D. N.D. BPYM^(d) 26.7 39 Co₂(CO)₈— 1,3- 90 3.5^(b) P 27.9 7.1 0.3 27.761 34 Ru₃(CO)₁₂ dioxolane^(f) W/W N.D. N.D. N.D. BPYM 27.7 Me₂Cl₁₂H₂₅N40 Co₂(CO)₈— 1,3- 90 2.75^(b) P^(h) 27.9 4.1 2.4 16.6 36 20 Ru₃(CO)₁₂dioxolane W/W N.D. N.D. N.D. BPYM^(d,g) 16.6 ^(a)A repeat of Run24090-143, using new batch of BPYM (#2) ^(b)Run with ½ (CO/H₂) gas^(c)Double 1,3-dioxolane solvent also ^(d)No promoter ^(e)More HPA,CH₃CHO, C2H5CHO and acrolein, less EtOH, in -191 versus -143 ^(f)Crude(99%) 1,3-dioxolane solvent ^(g)BPYM sample 23768-45 ^(h)Someprecipitated solids in product phase

 

TABLE 7 Time PDO PDO PDO EO Uptake Product Conc. (%) Production Sel.Yield EXP. Catalyst Solvent Temp ° C. (hrs) Phases wt (g) PDO HPA(mmole) (%) (mole %) 41 Co₂(CO)₈— 1,3-  90^(b) 4 P^(c) 27.9 7.9 0.3 31.064 38 Ru₃(CO)₁₂ dioxolane W/W N.D. N.D. N.D. BPYM^(a) 31.0 42 Co₂(CO)₈—1,3-  90^(b) 4.25 P 27.5 8.0 0.2 32.5 67 41 Ru₃(CO)₁₂ dioxolane^(d) W/WN.D. N.D. N.D. BPYM^(a) 32.5 43 Co₂(CO)₈— 1,3-  90^(e) 4.5 P^(c) 28.710.4 0.4 39.4 61 49 Ru₃(CO)₁₂ dioxolane W/W N.D. N.D. N.D. BPYM^(a) 39.444 Co₂(CO)₈— Me₂-1,3- 90 3.5 P^(c) 23.9 5.9 ^(g) 23.8  58^(g) 36Ru₃(CO)₁₂ Dioxolane W/W 4.6 ^(g) 4.0 BPYM^(f) 27.8 45 Co₂(CO)₈— 4-Me-1,390 3.5 P 25.1 5.5 N.D. 21.8 44 26 Ru₃(CO)₁₂ dioxolane W/W N.D. N.D. N.D.BPYM^(f) 21.8 46 Co₂(CO)₈— 2-Me- 90 4 P 26.3 6.9 1.2 24.4 47 29Ru₃(CO)₁₂ 1,3- W/W 0.4 N.D. 0.3 BPYM^(f) dioxolane 24.7 47 Co₂(CO)₈—Propy- 90 1.25^(h) P 29.4 <0.1 0.8 N.D. N.D. <0.1 Ru₃(CO)₁₂ lene W/W N.DN.D. N.D. BPYM^(f) Carbonate N.D. ^(a)No promoter ^(b)Run at 1800 psi(12,410 kPa) with ¼ (CO/H₂) syngas ^(c)Some precipitated solids inproduct phase ^(d)Crude (99%) 1,3-dioxolane solvent ^(e)Run at 1800 psi(12,410 kPa) with ½ (CO/H₂) syngas ^(f)Added Et₃N promoter ^(g)HPAeluted on GC with solvent ^(h)Stirrer belt broke during catalystpreparation step

 

TABLE 8 Time PDO PDO PDO EO Uptake Product Conc. (%) Production Sel.Yield EXP. Catalyst Solvent Temp ° C. (hrs) Phases wt (g) PDO HPA(mmole) (%) (mole %) 48 Co₂(CO)₈— 1,3- 90^(b) 4 P^(c) 28.1 9.5 0.3 37.365 47 Ru₃(CO)₁₂ dioxolane W/W N.D. N.D. N.D. BPYM^(a) 37.3 492[Co₂(CO)₈— 1,3- 90  2.5 P^(c) 28.4 6.4 1.5 27.5 43 34 Ru₃(CO)₁₂dioxolane W/W N.D. N.D. N.D. BPYM]^(a) 27.5 50 Co₂(CO)₈— 1,3- 90^(e) 4.5P^(c) 28.2 8.9 0.4 36.1 63 43 Ru₃(CO)₁₂ dioxolane W/W N.D. N.D. N.D.BPYM^(a,d) 36.1 51 Co₂(CO)₈— 1,3- 90^(f) 3.75 P^(c) 28.3 10.4 0.2 40.259 49 Ru₃(CO)₁₂ dioxolane W/W N.D. N.D. N.D. BPYM^(a) 40.2 ^(a)Nopromoter ^(b)Run at 2000 psi (13,790 kPa) with ¼ (CO/H₂) syngas ^(c)Someprecipitated solids in product phase ^(d)Using new batch of BPYM (#3)^(e)Run at 1800 psi (12,410 kPa) with ½ (CO/H₂) syngas ^(f)Run at 2000psi (13,790 kPa) with ½ (CO/H₂) syngas

 

TABLE 9 Time PDO PDO PDO EO Uptake Product Conc. (%) Production Sel.Yield EXP. Catalyst Solvent Temp ° C. (hrs) Phases wt (g) PDO HPA(mmole) (%) (mole %) 52 Co₂(CO)₈— 1,3- 90^(b) 3.25 P 28.9 5.0 4.2 20.331 25 2[Ru₃(CO)₁₂ dioxolane W/W N.D. N.D. N.D. DIPY]^(a) 20.3 53Co₂(CO)₈— 1,3- 90^(b) 4 P^(c) 29.0 11.3 4.1 46.0 57  54^(d) 2[Ru₃(CO)₁₂dioxolane W/W^(c) N.D. N.D. N.D. DIPY] 46.0 Me₂C₁₂H₂₅N ^(a)No promoter^(b)Run at 2000 psi (13,790 kPa) with ¼ (CO/H₂) syngas ^(c)Black solidsin reactor and water wash ^(d)Approximate PDO + HPA yield: 74%

 

TABLE 10 Time PDO PDO PDO EO Uptake Product Conc. (%) Production Sel.Yield EXP. Catalyst Solvent Temp ° C. (hrs) Phases wt (g) PDO HPA(mmole) (%) (mole %) 54 Co₂(CO)₈— MTBE 90^(b) 2 P 18.7 0.2 0.5 0.8 N.D. 1.3 Ru₃(CO)₁₂- W/W 0.5 N.D. 0.3 ½ TPTZ 1.1 55 Co₂(C6O)₈— 1,3- ″ 4.75 P29.1 10.6¹ N.D. 44.0 79 51 2[Ru₃(CO)₁₂- dioxolane W/W N.D. N.D. N.D.TPTZ]^(a) 44.0 56 Co₂(CO)₈— 1,3- ″ >3 P 27.4 2.15 0.3 4.6 61  5.7^(e)2[Ru₃(CO)₁₂- dioxolane W/W^(f) 0.2 <0.1 0.2 TPTZ]^(c) 4.8^(e) 57Co₂(CO)₈— 1,3- ″ 4 P 27.7 4.0 0.1 13.8 67 19^(e) 2[Ru₃(CO)₁₂- dioxolaneW/W 0.3 N.D. 0.2 TPTZ]^(d) 14.0^(e) 58 Co₂(CO)₈— 1,3- ″ G P 26.9 4.0<0.1 12.6 73 23^(e) 2[Ru₃(CO)₁₂- dioxolane W/W h h h TPTZ]^(a) 12.6^(e)59 11/2 1,3- ″ 4.75 P 28.4 9.8 0.1 34.3 76 45^(e) [Co₂(CO)₈— dioxolaneW/W 1.1 N.D. 0.7 2{Ru₃(CO)₁₂- 35.0 TPTZ}]^(a) 60 Co₂(CO)₈— 1,3- ″ 5.25 P28.2 12.9 0.1 40.6 80 54^(e) 2[Ru₃(CO)₁₂ dioxolane W/W 1.5 N.D. 1.0¾TPTZ]^(a) 41.6 ^(a)Co—Ru-Ligand pretreatment at 90° C. ^(b)Run at 2000psi (13,790 kPa) with ¼ (CO/H₂) syngas ^(c)Co—Ru-Ligand pretreatment at130° C. ^(d)Co—Ru-Ligand pretreatment at 110° C. ^(e)New glc column andnew PDO response factor ^(f)Some solids in water wash phase ^(g)A repeatof Run 24285-117 in ir cell ^(h)No water wash in this run ^(i)Confirmedby gc-ir/ms, plus ethanol, 1-propanol, 3-(2-hydroxyethoxy)-1-propanol,(3-hydroxypropyl)-3-hydroxypopionate

 

TABLE 11 Time PDO PDO PDO EO Uptake Product Conc. (%) Production Sel.Yield EXP. Catalyst Solvent Temp ° C. (hrs) Phases wt (g) PDO HPA(mmole) (%) (mole %) 61 Co₂(CO)₈— 1,3- 90^(b) 5.25 P 26.9 5.5 N.D. 22.773 29^(c) 2[Ru₃(CO)₁₂- dioxolane W/W 0.7 N.D. 0.5 ¾TPTZ]^(a) 23.2 62Co₂(CO)₈— 1,4- ″ 5.5 P 28.5 13.9 0.1 47.5 76 59^(c) 2[Ru₃(CO)₁₂- dioxaneW/W 1.7 N.D. 1.2 ¾TPTZ]^(a) 48.7 63 2[CO₂(CO)₈— 1,3- ″ 5.5 P 29.9 11.60.1 45.9 71 57^(c) 2{Ru₃(CO)₁₂- dioxolane W/W^(e) 1.1 N.D. 0.8TPTZ}]^(a) 46.7 64 Co₂(CO)₈— 1,3- ″ 5.25 P 28.5 12.7 0.3 40.7 78 52^(c)2[Ru₃(CO)₁₂- dioxolane W/W 1.4 N.D. 1.0 ½TPTZ]^(a) 41.7 65 Co₂(CO)₈—2-Et-2-Me- ″ 6.5 P^(h) 24.8 5.8 0.4 22.6 66 35 2[Ru₃(CO)₁₂- DioxolaneW/W 8.1 N.D. 5.7 ¾TPTZ)^(a) 28.3 66 2[Co₂(CO)₈— 1,3- ″ F P f 4.3 0.514.0 61 29 2{Ru₃(CO)₁₂- dioxolane W/W g g g TPTZ}]^(a) 14.0 67¾[Co₂(CO)₈— 1,4- ″ 6 P 27.8 10.6 N.D. 29.5 66 47 2{Ru₃(CO)₁₂ dioxane W/W1.0 N.D. 0.8 3/4TPTZ}]^(a) 40.3 ^(a)Co—Ru-Ligand pretreatment at 90° C.^(b)Run at 2000 psi (13,790 kPa) with ¼ (CO/H₂) syngas ^(c)New glccolumn and new PDO response factor ^(d)A repeat run, very similarresults ^(e)Small amount of solids in water wash ^(f)A repeat of run24285-167 in ir cell ^(g)No water wash in this run ^(h)Some solids inthe reactor

 

TABLE 12 PDO PDO PDO Product Conc. (%) Production Sel. Yield EXP.Catalyst Solvent Temp ° C. Phases wt (g) PDO HPA (mmole) (%) (mole %) 68Co₂(CO)₈— MTBE 80^(c) P 19.1 0.3 3.7 1.3 N.D. 3.7 [Ru₂(CO)₄— W/W 2.417.0. 2.0 (MeCOO) (1,10- 3.3 PHEN)₂]^(+a) 69 Co₂(CO)₈— ″ 80^(c) P 18.20.4 3.2 1.3 N.D. 4.3 [Ru₂(CO)₄— W/W 2.6 17.3 2.3 (MeCOO) (1,10- 3.6 70Co₂(CO)₈— ″ 80^(c) P 18.4 0.3 5.0 1.5 N.D. 2.1 [Ru₂(CO)₄— W/W 0.4 9.10.4 (MeCOO) (1,10- 1.9 PHEN)]^(+d) 71 Co₂(CO)₈— ″ 90 T 18.3 1.4^(e) 0.14.6 26 13 Ru₃(CO)₁₂- B 1.2 32.2 0.7 2.7 48 ½ Bipyrimidine W/W 4.5 0.23.0 10.3 72 Co₂(CO)₈— ″ 90^(c) P 19.1 1.1 0.1 4.4 29 7.3 Ru₃(CO)₁₂- W/W2.8 0.2 1.7 ½ Dipyridyl 6.1 73 Co₂(CO)₈— ″ 90^(c) P^(f,g) 19.5 0.3^(e)0.6 1.2 N.D. 1.8 Ru₃(CO)₁₂- W/W 1.0 3.4 0.8 ½ Biquinoline 2.0^(a)Product 24090-75A, made at 70° C. ^(b)Product 24090-75B, made at 30°C. ^(c)Run with ½ (CO/H₂) gas ^(d)Product 24090-93 ^(e)Checked by PDOspiking ^(f)Some black precipitate in liquid product mix ^(g)Larger EOaddition than usual

 

TABLE 13 PDO PDO PDO Product Conc. (%) Production Sel. Yield EXP.Catalyst Solvent Temp ° C. Phases wt (g) PDO HPA (mmole) (%) (mole %) 74Co₂(CO)₈— MTBE 90^(a) P^(c) 19.2 1.4 0.1 5.3 N.D. 7.6 Ru₃(CO)₁₂-½ W/W1.4 0.2. 0.9 4,4′ Me₂-2,2′- 6.2 Dipyridyl 75 Co₂(CO)₈— ″ 90^(a) P^(b)19.0 0.2 0.6 0.6 N.D. 0.7 Ru₃(CO)₁₂-½ W/W N.D. N.D. N.D.2,2′-Dipyridylamine 0.6 76 Co₂(CO)₈— ″ 90^(a) P^(b) 18.6 <0.1 0.6 0.4N.D. 0.5 Ru₃(CO)₁₂- W/W N.D. N.D. N.D. ½ Di-2- 0.4 77 Co₂(CO)₈— ″ 90^(a)P 19.0 0.9 0.3 3.8 N.D. 6.8 Ru₃(CO)₁₂- W/W(T) 2.6 0.9 1.5 ½ 1,10-PHENW/W(B)^(d) 3.1 1.2 0.4 5.7 78 Co₂(CO)₈— ″ 90^(a) P 19.1 1.1 0.1 3.8 N.D.6.8 Ru₃(CO)₁₂- W/W^(d) 2.7 0.1. 1.9 ½ 4,7-Me₂PHEN 5.7 79 Co₂(CO)₈— ″90^(a) P 19.0 0.9 <0.1 3.3 N.D. 7.8 Ru₃(CO)₁₂- W/W^(d) 4.6 0.2 3.1 ½5,6-Me₂PHEN 6.4 80 Co₂(CO)₈— ″ 90^(a) P 18.7 0.2 0.9 0.9 N.D. 1.6Ru₃(CO)₁₂- W/W^(d) 0.6 2.0. 0.4 Pyrimidine 1.3 ^(a)Run with ½ (CO/H₂)gas ^(b)Considerable black precipitate in reactor at end of run^(c)Considerable hard reddish precipitate in reactor at end of run^(d)Solid suspension in this water wash phase

 

TABLE 14 PDO PDO PDO Product Conc. (%) Production Sel. Yield EXP.Catalyst Solvent Temp ° C. Phases wt (g) PDO HPA (mmole) (%) (mole %) 81Co₂(CO)₈— MTBE 90^(a) P 19.0 0.2 0.9 0.8 N.D. 1.3 Ru₃(CO)₁₂- W/W^(b) 0.52.2 0.4 Pyridazine 1.2 82 Co₂(CO)₈— ″ 90^(a) P 18.4 0.2 0.8 0.8 N.D. 1.9Ru₃(CO)₁₂- W/W^(b) 0.9 2.7 0.7 Quinazoline 1.5 83 Co₂(CO)₈— ″ 90^(a) P18.6 0.2 0.4 1.0 N.D. 1.8 Ru₃(CO)₁₂- W/W^(b) 0.6 1.1 0.5. ½ Neocuproine1.5 84 Co₂(CO)₈— THF 100^(a,c) P 21.3 0.1 1.4 0.6 N.D. 1.3 Ru₃(CO)₁₂-W/W^(d) N.D. N.D. N.D. ½ 2,2′- 0.6 Dipyridylamine 85 Co₂(CO)₈— MTBE90^(a) P^(e) 18.5 0.2 1.1 0.9 N.D. 2.3 Ru₃(CO)₁₂- W/W^(b) 2.6 1.1 1.1 ¼3,6- 2.0 Dipyridyl- tetrazine 86 Co₂(CO)₈— ″ 90^(a) P 18.7 0.2 0.5 0.8N.D. 1.3 Ru₃(CO)₁₂- W/W^(b) 0.5 N.D. 0.3 ¼ 2,4,6- 1.1 Tripyridyl-S-Triazine 87 Co₂(CO)₈— ″ 90^(a) P^(e) 19.5 0.1 2.1 0.5 N.D. 0.6Ru₃(CO)₁₂- W/W^(b) N.D. N.D. N.D. ½ 2,2:6,2- 0.5 Terpyridine ^(a)Runwith ½ (CO/H₂) gas ^(b)Solid suspension in water wash phase ^(c)Half theusual EO charge ^(d)Small amount of solids in water wash phase ^(e)Somesolids in product phase

 

TABLE 15 PDO PDO PDO Product Conc. (%) Production Sel. Yield EXP.Catalyst Solvent Temp ° C. Phases wt (g) PDO HPA (mmole) (%) (mole %) 88Co₂(CO)₈— THF 90^(a) P 22.9 0.2 0.5 0.8 N.D. 1.0 Ru₃(CO)₁₂- W/W^(b) N.D.N.D. N.D. ½ 3,6-Dipyridyl- 0.8 tetrazine 89 Co₂(CO)₈— MTBE 90^(a) P^(c)18.8 0.1 1.0 0.5 N.D. 0.6 Ru₃(CO)₁₂- W/W^(b) N.D. N.D. N.D. ½ 2,3- 0.5Bis(Pyridyl) pyrazine 90 2[Co₂(CO)₈— THF 90^(a) P 23.9 0.1 N.D. 0.4 N.D.0.5 Ru₃(CO)₁₂]- W/W N.D. N.D. N.D  ½ 3,6-Dipyridyl- 0.4 tetrazine 91Co₂(CO)₁₂ MTBE 90^(a) P 19.6 0.3 0.5 1.1 N.D. 1.3 Ru₃(CO)₁₂- W/W^(b)N.D. N.D. N.D. ½ 3-Pyridyl-5,6- 1.1 diphenyl triazine^(d) ^(a)Run with ½(CO/H₂) gas ^(b)Solid suspension in water wash phase ^(c)Some solids inproduct phase ^(d)Catalyst prep 3 days before run

 

TABLE 16 PDO PDO PDO Product Conc. (%) Production Sel. Yield EXP.Catalyst Solvent Temp ° C. Phases wt (g) PDO HPA (mmole) (%) (mole %) 92Co₂(CO)₈— MTBE 90 P 18.5 0.2 1.1 0.9 N.D. 2.3 Ru₃(CO)₁₂-3,6- W/W 1.62.6. 1.1 Dipyridyl- 2.0 tetrazine 93 Cu₂(CO)₇— ″ 90 P 19.5 0.1 2.1 0.5N.D. 0.6 Ru₃(CO)₁₂- W/W N.D. N.D. N.D. 2,2:6,2- 0.5 Terpyridine 94Co₂(CO)₈— THF 90 P 22.9 0.2 0.5 0.8 N.D. 1.0 Ru₃(CO)₁₂-3,6- W/W N.D.N.D. N.D. Dipyridyl- 0.8 tetrazine 95 Co₂(CO)₈— MTBE 90 P 19.6 0.3 0.51.1 N.D. 1.3 Ru₃(CO)₁₂-3-(2- W/W N.D. N.D. N.D. Pyridyl)-5,6- 1.1Diphenyl 1,2,4-Triazine 96 Co₂(CO)₈— 1,3- 90 P 27.7 3.7 1.7 14.7 N.D. 18Ru₃(CO)₁₂- dioxolane W/W N.D. N.D. N.D. 3,6-Dipyridyl- 14.7 tetrazine 97Co₂(CO)₈— 1,3- 90 P 28.0 2.3 5.4 6.9 N.D. 8.5 Ru₃(CO)₁₂- dioxolane W/W0.2 0.7 0.1 3-Pyridyl-5,6- 7.0 Diphenyl Triazine Disulfonic acid salt 98Co₂(CO)₈— 1,3- 90 P 29.0 47.4 1.5 11.7 N.D. >20 Ru₃(CO)₁₂- dioxolane +W/W 6.9 0.2 4.8 3-Pyridyl-5,6- 1,3-PDO 16.5 Diphenyl Triazine Disulfonicacid salt

 

TABLE 17 Time PDO PDO PDO Temp EO Uptake Product Conc. (%) ProductionSel. Yield EXP. Catalyst Solvent ° C. (hr) Phases wt (g) PDO HPA (mmole)(%) (mole %)  99 Cu—RuCl₂ MTBE 90 3 P 18.4 N.D. N.D. N.D. N.D. <0.1(C₁₀H₈N₂)₂-2H₂O W/W N.D. 0.1 N.D. <0.1 100 Co—Ru₃(CO)₁₂- MTBE 90  3¼ P19.9 0.4 0.2 1.2 N.D. 1.4 2,2-Bipyridyl W/W N.D. 0.8 N.D. 1.2 101Co—Ru₃(CO)₁₂- MTBE 100 3 P 19.3 N.D.^(a) 0.1 N.D. N.D. <0.1Et₂NCH₂CH₂NEt₂ W/W N.D. N.D. N.D. <0.1 102 Co—Ru₃(CO)₁₂- MTBE 100  2¾ P19.0 N.D. N.D. N.D. N.D. <0.1 Me₂NCH₂CH₂NMe₂ W/W N.D. N.D. N.D. <0.1 103Co—Ru₃(CO)₁₂- MTBE 100  3¾ P 18.8 0.3 0.3 0.9 N.D. 1.0 C₁₀H₉N₃ ^(b) W/WN.D. N.D. N.D. 0.9 104 Co- MTBE 80 3 P 19.1 N.D. 0.4 N.D. N.D. <0.11½Ru₃(CO)₁₂- W/W N.D. N.D. N.D. 1.2(C₄H₈)NCH₂ <0.1 CH₂N(C₄H₈)^(c) 105½Co₂(CO)₈— MTBE >80 d P d N.D. 0.8 N.D. N.D. <0.1 Ru₃(CO)₁₂- <0.1 ½2,2-Bipyridyl^(d) ^(a)Numerous other product peaks ^(b)2,2′Dipyridylamine^(c)1,2-Dipyrrolidinoethane Sample 23768-34 ^(d)Run in in-situ IR cell,solution spectra recorded

 

TABLE 18 Time PDO PDO PDO Temp EO Uptake Product Conc. (%) ProductionSel. Yield EXP. Catalyst Solvent ° C. (hr) Phases wt (g) PDO HPA (mmole)(%) (mole %) 106 Co₂(CO)₈— MTBE 90   3¼ P 19.9 0.4 0.2 1.2 N.D. 1.4Ru₃(CO)₁₂-1.7 W/W N.D. 0.8 N.D. DIPY 1.2 107 Co₂(CO)₈— MTBE 90   2¾ P19.1 1.1 0.1 4.4 29 7.3 Ru₃(CO)₁₂-DIPY W/W 2.8 0.2 1.7 6.1 108 Co₂(CO)₈—THF 90^(a) 3 P 23.5 0.8 3.4 3.6 N.D. 4.2 Ru₃(CO)₁₂-DIPY W/W N.D. N.D.N.D. 3.6 109 Co₂(CO)₈— THF 100^(a,b) ¾ P 22.2 N.D. 1.5 N.D. N.D. <0.1Ru₃(CO)₁₂-DIPY W/W N.D. N.D. N.D. N.D. 110 Co₂(CO)₈— PDO 90^(a) 1 P 25.685.5 0.1 e N.D. e Ru₃(CO)₁₂-DIPY W/W 19.6 N.D. e e 111 Co₂(CO)₈— THF^(c)90^(a)  1¼ P 23.1 0.6 4.3 2.6 N.D. N.D. Ru₃(CO)₁₂-DIPY W/W N.D. N.D.N.D. 2.6 112 Co₂(CO)₈— THF^(c) 90^(a) 3 P 24.3 0.1 0.7 0.4 N.D. 0.5[Ru₃(CO)₁₀ W/W N.D. N.D. N.D. (BIPY)]^(d) 0.4 ^(a)Run with ½ (CO/H₂) gas^(b)Half the usual EO charge ^(c)Uninhibited THF solvent ^(d)Product24090-155 ^(e)Run in PDO, No PDO yield calculations

 

TABLE 19 Time PDO PDO PDO Temp EO Uptake Product Conc. (%) ProductionSel. Yield EXP. Catalyst Solvent ° C. (hr) Phases wt (g) PDO HPA (mmole)(%) (mole %) 113 Co₂(CO)₈— 1,3- 90^(a) 2 P 27.6 2.1 3.4 7.9 29 9.7Ru₃(CO)₁₂-DIPY Dioxolane W/W^(b) N.D. N.D. N.D. 7.9 114 2[CO₂(CO)₈— THF90^(a)  2½ P 23.6 1.0 2.1 3.6 N.D. 4.5 Ru₃(CO)₁₂-DIPY W/W N.D. N.D. N.D.3.6 115 Co₂(CO)₈— 1,3- 90  3 P 28.2 3.4 6.3 13.3 22 16 2[Ru₃(CO)₁₂-Dioxolane W/W N.D. N.D. N.D. DIPY] 13.3 116 2[Co₂(CO)₇— 1,3- 90  2 P52.9 1.2 4.1 7.6 16 9.3 2(Ru₃(CO)₁₂- Dioxolane W/W^(b) N.D. N.D. N.D.DIPY)] 7.6 117 Co₂(CO)₈— 1,3- 90^(a) 4 P 28.0 6.3 3.8 23.7 42 312[Ru₃(CO)₁₂- Dioxolane W/W N.D. N.D. N.D. DIPY]^(c) 23.7 118 Co₂(CO)₈—1,3- 90^(d)  2¾ P 28.3 6.0 2.7 25.1 43 31 2[Ru₃(CO)₁₂- Dioxolane W/WN.D. N.D. N.D. DIPY]^(c) 25.1 ^(a)Run with ½ (CO/H₂) gas ^(b)Smallamount of solids in water wash ^(c)No promoter ^(d)Run at 1800 psi with1/4 (CO/H₂) Syngas

 

We claim:
 1. A process for preparing 1,3-propanediol comprising thesteps of: (a) contacting, in a reaction mixture, ethylene oxide, carbonmonoxide, hydrogen, an inert reaction solvent, and a catalystcomposition comprising: (i) one or more non-ligated cobalt carbonylcompounds; and (ii) a N-heterocyclic-ligated ruthenium carbonylcompound; and (b) heating said mixture to a temperature of from 30 to150° C. and a pressure of from 100 to 4000 psi (690 to 27,580 kPa) for atime effective to produce a two-phase reaction product mixturecomprising an upper phase comprising a major portion of the solvent, atleast 50 wt % of the catalyst composition, plus unreacted ethyleneoxide, and a lower phase, which comprises a major portion of1,3-propanediol.
 2. The process of claim 1, wherein the hydrogen tocarbon monoxide molar ratio is from 1:1 to 8:1.
 3. The process of claim1, wherein the hydrogen to carbon monoxide molar ratio is from 2:1 to6:1.
 4. The process of claim 1, further comprising the catalyst is madeby a step-wise method wherein all the components are brought together atthe same time under synthesis gas conditions.
 5. The process of claim 1further comprising the ruthenium compound is reacted with theN-heterocyclic ligand in the presence of syngas.
 6. The process of claim1 further comprising the ruthenium compound is reacted with theN-heterocyclic ligand at a temperature in the range of 25 to 150° C. 7.The process of claim 1 further comprising that theruthenium-N-heterocyclic ligand complex is caused to undergo a redoxreaction with the cobalt compound at a temperature in the range of 25 to150° C.